Preparation of organic nitrogenous base salts



Patented Apr; 1, 1941 UNITED, STATES PATENT OFFICE or ORGANIC m'mocnnou .BASE ssn'rs PREPARATION Frank J. Cahn and Morris B. Katnnan, Chicago,

Ill., assignors to The Emulsol Corporation, Ohicago, Ill., a corporation Illinois No Drawing. Application January 5, 1940,

Serial No. 312,500

'11 Claims. (01. 260-401) monoethanolamine (potassium salt) with an ormethods of This invention relates to novel preparing chemical compounds.

More specifically, the invention is concerned with the preparation of organic nitrogenous base salts of interface modifying agents in the form of derivatives, particularly esters, of lipophile materials such as higher molecular weight fatty acids and higher molecular weight alcohols,

wherein said agents containat least one acid function in unesterifled form which retains its salt-forming capacity. These include, for example, sulphates, sulphonates, phosphates, borates, phthalates, succinates, maleats, fumarates, ta'rtrates, citrates, azelaiates, oxalates, malonates, sebacates, mellitates,, mucates, saccharates, and-other salt-forming polybasic acid derivatives, especiallyi esters, of lipophile materials. The invention is concerned with a novel and eftective process for producing organic nitrogenous base salts ofsuch and similar derivatives.

Various of these compounds including, for example, sulphates, sulphonates', phosphates and borate derivatives hi lipophile materials such as higher molecular weight fatty acids and alcohols have been heretofore produced, as shown; for example, in the following United States Patents: 1,897,741; 1,917,250; 1,917,255; 1,968,793; 1,968,- 794; 1,968,796; 1,968,797; 2,006,309; 2,023,387; 2,028,091; 2,052,027; 2,077,005; 2,026,785; 2,052,- 029; 2,053,653; 2,094,489; and 2,178,139. In certain cases, it has already been proposed to produce alkylolamine and amine salts of sulphates oi higher "molecular weight alcohols. It has been found, however, that such compounds and others, not heretofore known, may be prepared in'a relatively simple and expeditious manner,

all as more fully pointed out hereinafter.

In general, the organic nitrogenous base salts,

particularly the alkylolamine'salts, oi the com-.

pounds herein contemplated are more readily soluble in cold water than the corresponding alkall metal or ammonium salts and, for certain purposes, the preparation of compounds which are soluble in cold water to the extentot at least several percent or at least 5%, and from 15% to 25%, is quite important. A

The novel method oi the present'invention, generally speaking. comprises reacting an alkali preferably metal or similar salt of a sulphonic, sulphuric or oxygenated sulphur, phosphorus, boron, or other derivative of a lipophile material suchas a higher molecular weight fatty acid or alcohol, for-example, lauryl potassium sulphonate, or the sulpboacetic acid amide of-the lauric acid ester of game nitrogenous base such as monoethanolamine, and with a compound which reacts with the cationic constituent of the lauryl potassium sulphonate, or the sulpho-acetic acid amide of the lauric acid ester of 'monoethanolamine (potassium salt) to produce a compound more insoluble than the lauryl potassium sulphonate,

or the sulphoaceticacid amide of the lauric acid ester of monoethanolamine (potassium salt),

whereby the more insoluble compound precipitates out and may be removed by filtration or the like, leaving the monoethanolamine salt of lauryl sulphonate, or the sulphoacetic acid amide of the lauric acid ester of monoethanolamine (monoethanolaminesalt) as the case may be, in solution from which it can, ifv desired, be recovered by evaporation or drying of the solution.

More specifically, unusually good results may be obtained by reacting a sulphonate, sulphate, phosphate, borate or other derivative of a higher The reaction takes place when the alkali metal or similar salt of the sulphon'ic, sulphuric or oxygenated sulphur, phosphorus, boron or other derivative is more soluble or less insoluble than the salt or the like such as potassium acid tartrate which forms during the reaction.

In order to enable those skilled in the art to understand the nature of the invention even more fully, the following examples are given by way of illustration. It will be understood, however, that the speciilc reactants, the proportions thereof, and the times and temperatures may be varied within limits without ,departing from the I spirit of the invention. The examples, therefore, are to be taken in an illustrative rather than in a limitative sense, the scope of the invention being pointed out in the claims.

Example I A. 200 grams of crystalline lauryl potassium sulphoacetate, prepared from commercial lauryl alcohol, were dissolved in 400 cc. of water at 80 degrees C. to produce a relatively stiff paste.

B. 150 grams of tartaric acid and 141 grams of triethanolamine were dissolved in 400 cc. of water.

C. Compositions A and B were then stirred together at a temperature of about 90 degrees C. A heavy precipitate came down and the previously viscous mixturebecame quite mobile. The precipitate, which comprised potassium acid tartrate, was filtered off and the filtrate was then neutralized with 50 grams of triethanolamine. The final solution was quite viscous. containing in the neighborhood of 20% of lauryl triethanolamine sulpho-acetate.

Example II 18.3 grams of dodecyl potassium sulphonate (C12H25-SO3K) containing 79% solids mol) were dissolved in 30 cc. of boiling water whereby a relatively stiff paste was formed. To said paste was then added a hot solution of 8.3 grams of tartaric acid and 3.45 grams of monoethanolamine in 45 cc. of water. The stiff paste thereupon became limpid and potassium acid tartrate precipitated out. The mass was then cooled to 0 C. and filtered on a Buchner funnel and the filtrate was neutralized with 0.4 gram of monoethanolamine using litmus as an indicator. The final solution weighed 78 grams and contained 20% by weight of monoethanolamine lauryl sulphonate C IhOH C zHz5S O 3NH The solution had excellent sudsing, foaming, lathering and detergent properties rendering it useful, among other things, for shampoos,- hair washes and the like. At temperatures as low as 3 C., there was no precipitation. At lower temperatures, a slight cloudiness or turbidity appeared which, however, disappeared on warmin the solution to room temperature.

Example III 133 grams of potassium lauryl sulpho-acetate were dissolved in 700 cc. of boiling water and the resulting solution was then mixed with a previously prepared solution containing 69 grams of tartaric acid, 36.6 grams of pyridine and 200 cc. of water. The two solutions were mixed at a temperature of-about 90 degrees C. and were then allowed to cool to room temperature whereupon the resulting solution was filtered from the potassium acid tartrate which had precipitated out.

Approximately I80 cc. of a yellow colored limpid solution were obtained which had excellent foamtion was then neutralized to a methyl red yellow with 20 grams of piperidine. A water-white viscous liquid was obtained possessing strong foaming properties in alkaline or acid aqueous media as well as in hard water. The solution contained the piperidine salt of lauryl sulpho-acetate.

' Example V The resulting solution was then allowed to cool for about a day at room temperature and was then decanted and filtered from the precipitate of potassium acid tartrate, the latter then being washed with 50 cc. of water and the wash water being added to the filtrate.

To the approximately 2660 grams of solution thus obtained, about 20 grams of monoethanolamine were added until methyl red gave a yellow color. The resulting solution contained a substantial proportion of the monoethanolamine salt of lauryl sulphoacetate.

Example VI An aqueous solution of 8.1'parts, by weight, of acid methylpyridinium tartrate in 17 parts, by weight, of water was prepared by mixing one mol of 0.166 normal methylpyridinium hydroxide solution with an aqueous solution of one mol of tartaric acid and evaporating down. This solution was then heated to a temperature of about 90 degrees C. and was then added to a previously heated solution, also at about 90 degrees 0., containing 10.4 parts, by weight, of lauryl potassium sulpho-acetate and 50 parts, by weight, of water.

' The mass was permitted to cool to approximately 25 degrees C. and the acid potassium tartrate which had precipitated out was filtered oil. The

resulting clear filtrate was neutralized to yellow methyl red with 20 volume parts of 0.167 normal sulting solution, containing a substantial proportion of the methylpyridinium salt or lauryl sulpho-acetate, was water-white, viscous, -substantially odorless, and had excellent foaming propering properties in hard water as well as in the presence of alkalies and acids. The solution contained a substantial proportion of the pyridine salt of the sulpho-acetate of lauryl alcohol.

v Example IV ties in hard water as well as in aqueous acidulated media. It was very suitable for use as a hair wash or shampoo.

Example VII 432 grams of the lauric acid ester of the sulphoacetic acid amide of monoethanolamine (potassium salt), corresponding to the formula:

were dissolved in 1483 grams of water, at degrees C., and there was added thereto, with stirring, a solution of 213 grams oi tartaric acid in 213 cc. of water. There was then added thereto, with vigorous stirring, a solution of 88 grams of monoethanolamine in 88 cc. of water. The final product was cooled to about 20-degrees C. to 22 degrees C. and filtered to remove the precipitate or potassium acid tartrate which'formed during the reaction. To the clear, limpld ill-- trate, 11 cc. of monoethanolamine were added in order to neutralize the solution to a pH of about 6.0. The solution contained a substantial proportion of the monoethanolamine salt of the sulpho-acetic acid amide of the lauric acid ester veniently accomplished by making up the volume v of the clear limpid filtrate to 2750 cc. by the addition thereto of water and there were then added thereto, with stirring,1150-cc. of an aqueous solution containing 40% monoethanolamine. sulphate, namely, the sulphuric acid salt of monoethanolamine. The final product wasaclear, viscous materialwhich was very satisfactory as a shampoo base. I

Example VIII (1) 2000 grams of a product consisting essen-' tially of a compound having the following for- I being the acyl radical of coconut oilmixed'fatty acids,- comprising largely lauric acid), 735 grams of potassium metabisulphite (X28205) 370 grams *or potassium hydroxide and 2210 cc. of water were heated for hour at 90 degrees C. to 95 degrees C. The temperature rose to 100 degrees C. during the reaction; a total of 700 grams of crushed ice was added in order to control the temperature.

(2) To the reaction mass produced as described in part (1) hereof, 5000 cc. of water and 2364 grams of tartaric acid were added with constant stirring at a temperature of about 70 degrees C. There were then added, with stirring, 1000 grams of monoethanolamine.- The mass was allowed to cool to room temperature and the precipitate of potassium acid'tartrate, which had formed 7 during the reaction, was filtered oil. To1000 grams of the clear solution, 570 cc. of water and 1 188 cc. of monoethanolamine were added to bring the product to a pH of about 6.3. The resulting solution had foamingand detergent propamine were added thereto and mixed with the solution. The precipitate of potassium acid tartrate was filtered oil and, to the resulting illtrate, 12 grams of trlethanolaminewere added to bring the product up to a pH of about 6.0.

[The solution, which had good foaming and detergent properties, contained a substantial proportion of the triethanolamine salt of the sulphoacetic acid amide of the lauric acid ester of monoethanolamine, said compound having the following formula:

cnnsc o-cmrun-c i-cm-soinhacsmon i Instead of employing tartaric acid, as described above, oxalic acid and other acids such as perchloric acid or acids of organic character can be used whose alkali metal or other salts or acid salts are'more insoluble than the saltof the.

sulphonic acid derivative or the like employed as one of the reactants, at the concentrations and under the conditions of the reaction. Tartaric acid is preferred, however, because of the unusually low cold-water solubility of potassium acid tartrate.

If it is desired still further to decrease the solubility of the salt, such as potassium acid tartrate, methyl alcohol, ethyl alcohol or other organic solvents may be added to the reaction mixture to provide an environment in which the potassium acid tartrate or the like is even still more insoluble thanit is in cold water alone.

- The preferred compounds whose organic nitrogenous base salts may be produced in accordance with the novel teachings of, the present invention, as described hereinabove, are generally characterized by the presence of at least one higher molecular weight llpophile group containing preferably at least eight carbon atoms, preferably, although not necessarily, aliphatic in character, and by the presence of at least one hydrophile or hydrophillic group, preferably in the form of an oxygenated sulphur, phosphorus, boron,

arsenic or carbon radical; or the like, particularly sulphurin the form of sulphate or sulphonic acid radicals. Preferably, the llpophile and hydrophile groups are in a state of balance" whereby the resulting compound has the property of re-- means of a margarine frying test, as described in 'erties and contanied a substantial proportion of a compound having the following. formula:

has the same significance as described hereinabove) V Example IX '161 grams of the lauric acid ester of the sulphoacetic acid amide of monoethanoiamine (p0 tassium salt) were dissolved in 000 cc. of water at 60 degrees 0., 66 grams of tartaric acidw'ere added and the mass stirred until the tartaric-acid had dissolved, and then 62.5 grams of triethanolsaid patent, those skilled inthe art will in most cases, readily be able to predict the existenceoi "balance" from merely an inspection of the struc-. ture of the molecule of the compounds themselves. As a general rule. the hydrophile s nd llpophile groups should preferably be at the-ends or extremities of the molecule as, for example, in the case of lauryl monomethanolamine sul phate wherein the lauryl group or, in other words, the llpophile group, is present at one end of-the molecule, and the sulphate or hydrophile group is present at the other end of the molecule.

- It will be understood that the term "Lipophile groups" includes groups having a definite aillnity tor oils and fats and comprises, for example, alkyl,

aralkyl. aryl, ether or ester groups containing preferably at least eight carbon atoms. The llpophile group possesses predominantly hydrocarbon characteristics and, in general, is derived f.- om triglyceride fats and oils, waxes, mineral oils, other hydrocarbons, and the like. v

In contra-distinction thereto, the term hydrophile group" or "hydrophillic group includes groups which possess an ailinity for water and aqueous media and which, in the instant case, include, among others, the following: sulphate, sulphonic, phosphate, pyrophosphate, tetraphosphate, borate, lower molecular weight sulpho-carboxylic acids such as 'sulpho-acetates, sulphopropionates, sulpho-succinates, sulpho-citrates, sulpho-glutarates, polycarboxylic acids, hydroxypolycarboxylic acids, etc.

Among the oxygenated sulphur derivatives, several members of which have excellent sudsing, foaming, frothing, lathering. and detergent powers, are, as previously pointed out, the higher molecular weight alcohol sulphates and sulphonates. The alcohols from which these sulphates and sulphonates may be prepared include the following: aliphatic straight chain and branched chain alcohols such as hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, myristyl alcohol,

cetyl alcohol, oleyl alcohol, linoleyl alcohol, stearyl alcohol, ricinoleyl alcohol, palmitoleyl alcohol, melissyl alcohol, ceryl alcohol, carnaubyl alcohol, myricyl alcohol, branched chain octyl, decyl, dodecyl, tetra-decyl, hexadecyl and octadecyl aliphatic alcohols as, for example, 2-ethyl hexanol- 1, 2-n butyl octanol-l, 2-butyl tetra-decanol-l, and, in general, the higher molecular weight saturated and unsaturated aliphatic straight chain and branched chain alcohols. Preferably,

the alcohols which are utilized are, those corre- I -thenyl alcohol, borneol, menthyl alcohol, xylenols,

cresols, and such unsaturated alcohols as linalool, citronellol, geraniol and the like. Also included tially esterified or partially etherified sugars and sugar alcohols such as monolauric acid ester of sucrose, monostearic acid ester of dextrose, monopalmitic acid ester of mannitol, dicaproic acid ester of maltose, mono-octyl ether of sorbitol, monolaurylether of pentaerythritol, monolauric acid ester of pentaerythritol, and the like; the

" drogen of natural or hydrogenated animal or as, for example, the mixture of alcohols resulting from the hydrogenation of coconut oil or the free fatty acids of coconut oil. Lauryl alcohol comprises about 45% of the total alcohol mixture,

the remaining alcohols running from C5 to C15. Again, mixtures of alcohols such as are present in the so-called sperm oil alcohols, as well as those present in wool-fat, may equally efiicaciously be utilized. Indeed, these higher molecular weight alcohols are generally ofiered on the market in the form of mixtures of diiferent alcohols. If desired for any specific purpose, special fractions which predominate in a certain particular higher 7 molecular weight alcohol may be utilized or, if so within the class of alcohols which may be employed are such compounds as the hydroxy and alpha-hydroxy higher aliphatic and fatty acids as, for example, rlcinoleic acid, alpha-hydroxy stearic acid, alpha-hydroxy lauric acid, di-hyobtainable by substituting alkyl or acyl radicals.

preferably of high molecular weight, in place of the hydrogen of one or more hydroxy groups of polyhydroxy substances or polyhydric alcohols, it being understood that at least one hydroxy group attached to the nucleus of the polyhydroxy substance or polyhydric alcohol remains, are also within the scope of the alcohols from which the sulphates and sulphonates may be produced. As examples of such alcohols may be mentioned, pardesired, the products may be prepared from a single, substantially pure alcohol.

These sulphates and sulphonates, produced in accordance with the invention described hereinabove, may, in general, be represented by the formula wherein R is a radical containing a hydrocarbon chain of at least eight carbon atoms, X is a sulphuric or sulphonic group present at or near an extremity of the radical represented by R, and Y is an organic nitrogenous base cation.

In a still more specific aspect of this class of compounds, the suphates may be represented by the formula wherein R represents the residue of a normal primary alcohol containing from 8' to 18 carbon atoms, and Y represents an organic nitrogenous Benjamin R. Harris,

drophile group comprises oxygenated phosphorus insteadof oxygenated sulphur.- Among thesev aside fromjpatents referred to hereinabove, in

Patents Nos, 2,177,650 and 2,128,948 and in the following pending application: Application of 7 Serial No. 207,507, filed May 12, 1938.

Again, in place of either the oxygenated phosphorus or oxygenated sulphur-compounds, simi-' lar as,well as corresponding oxygenated boron compounds may be employed. These include boric acid esters of-higher molecular weight alcohols such as lauryl monoethanolamine borate, cetyl Pyridine borate, and .boric acid esters of monoglycerides of higher fatty acids such as monolaurin triethanolamine borate. For a more complete description rof boric acid derivatives, reference may be had to United States Patent .No, 2,052,192.

Another group of compounds whose organic nitrogenous base salts may be produced in accordance with the principles of the present invention are the lower molecular weight sulphocarboxylic acid esters of higher molecular weight alcohols such as those described hereinabove.

dine sulphoacetate, lauryl sulphoacetate monoethanolamine or triethanolamine. salt or other organic nitrogenous base salts such as those de- 1937, now Patent No. 2,185,455, issued January orthe like, and ui a small whole number, As illustrative of these compounds may be men- Among these compounds may be mentioned octyl pyri- Compounds of thegeneral type and othersof,

similar nature are disclosed in the following Unitd- States patents: 1,931,540; 1,932,177; 1,932,180;

, derived from higher molecular weight aliphatic,

2, 1940; and Patent Nos. 2,166,141} 2,166,142; and

Still another group of sulphonic and sulphate derivativeswhose organic nitrogenous base salts may be preparedin accordance with the teachings of the present invention are the compounds which correspond to the general formulae: R-C o-Nx..(YM

wherein R is an' aliphatic hydrocarbon radical containing at least 7 carbon atoms and preferably between 11 and 17 carbon atoms, xis hydrogen, n is either zero orone, Y is a lower molecular weight hydrocarbon oralkylene or substituted radical such as CzH4-, 'C:Hc-'-,

'-C4Hs or the like, or similar radicalsinterrupted by oxygen or sulphur in the chain, such as H 021 011 ems.

fatty, cyclo-aliphatic, aromatic, andv hydroaromatic acids, saturated and unsaturated, such as the following: caprylic acid, caproic acid, capric acid. behenic acid, arachidic acid, erucic acid, cerotic acid, melissic acid. stearic acid, oleic acid, rieinolelc acid, linoleic acid, linolenic acid, margaric acid, lauric acid, myristic acid, palmitic acid, mixtures of any two ormore of the above mentioned acids or other acids, mixed higher fatty acids derived from animal or vegetable sources.

for example, lard, coconut oil, sesame oil, corn oil, cottonseed oil, sardine oil, tallow, partially or. completelyhydrogenated animal and vegetable derived, by oxidation and otherfmethods, from petroleum; hydro-aromatic acids such as abietic acid; aromatic acids such as naphthoic acid, hy-

droxy aromatic acids such as hydroxy naphthoic acids, and the like. 1

Still another class of sulphonic derivatives whose organic nitrogenous base salts may be prepared in accordance with the teachings of the present invention are the sulphonated derivatives of alkylated or ara-lkylated polynuclear radicals.

hydrocarbons such as, for example, butyl naphtha'lene sulphonic acid monoethanoiamine salt, benzyl naphthalene sulphonic acid triethanolamine salt, iso-propyl naphthalene sulphonic acid pyridine salt, etc. Particularly contemplated are the organic nitrogenous base salts of those polynuclear derivatives, such as those of naphthalene, which contain alkyl, aralkyl or hydroaromatic radicals with three carbon atoms and upwards.

A further group of compounds whose organic nitrogenous base salts may be prepared in accordance with the principles of the present invention are higher molecular weight carboxylic acids and derivatives thereof wherein at least one hydrogen attached to the carbon atom adjacent to the carboxyl group of said carboxylic acids is replaced by a radical having strong hydrophillic properties comprising, for example, oxygenated sulphur and oxygenated phosphorus Examples of such compounds are as follows:

1 CH3(CH2)ii-CH-C o N3 Another group of compounds whose organic nitrogenous base salts may be prepared in accordance with the present invention, as indicated in Examples VII and IX, are those disclosed in the copending application of Morris B. Katzman, Serial No. 219,358, filed July 15, 1938, now Patent No, 2,184,770, issued December 26, 1939. At least most of the compounds disclosed in said application correspond to the following general formula:

wherein R is an organic radical containing at least four carbon atoms, alk and Z are each members selected from the class consisting of hydrocarbon radicals and substitution products thereof, Y is a member selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxyl, aralkyl, aryl, and alkylol, m and w are whole numbers, and X is a sulphonic radical.

A more'specific aspect of said compounds is represented by the general formula II RFC is an aliphatic acyl radical containing at least eight carbon atoms, alk is hydrocarbon, Y is a member selected from the group consisting of hydrogen, alkyl, oycloalkyl, alkoxyl, aralkyl, aryl, and alkylol, Z is a hydrocarbon residue, and X is a sulphonic group.

Additional groups of compounds which may be treated by means of the process of the present Serial Im ntor N0. Filed Albert K. Epstein oi: oi 222, 779 August 3, 1938, now Patent No. 2,198,806, issued April 30, 1940. Morris Katzman 255, 220 February 8. 1939. Albert K. Epstein 0t al l.. 285, 956 July 22, 1939. 1) o 280, 52 June 22, 1930. Morris B. Katzman 283,141 July 7, 1939. Morris Katzman 286, 777 July 27, 1939. Morris Kntzmau \t al 286, 776 July 27, 1939.

Do i 291, 898 August 25, 1939. Albert K. Epsii-in et aL... 296,918 September 23, 1939.

Representative compounds disclosed in said applications, whose organic nitrogenous base salts may be prepared in accordance with the process of the present invention, comprise the following:

CzHt-O-E-CHrS 01K Among the organic nitrogenous bases which may be employed in preparing the salts of the compounds in accordance with the present invention are, for example, alcohol amines and alkylolamines including monoethanolamine, diethanolamine, trlethanolamine, propanolamines, butanolamlnes, pentanolamines, hexanolamines, glycerolamines, diglycerolamines, derivatives of hydroxylamine, dibutyl ethanolamine, diethanol ethyl amine, cyclohexyl ethanolamine, alkylol polyamines such as alkylol derivatives of ethylene diamine, mono-methyl monoethanolamine, diethyl monoethanol'amine, l-amino-Z, 3-propanediol; 1,2-dlamino-propanol; dimethylol- -amino propane; trimethylol-amino methane; 2- methylamino-propan-diol-L3; 1 phenylamlnopropan-diol-2,3; 1-hydroxyethyl-amino-2, methoxy-propan-ol-3; 2-amino-2-methyl-1, 3-propanediol; 2 amino-2-n-propyl-1,3-propanediol; 2-amino-2-isopropyl-1, 3-propanediol; hydroxyamines, derived from various polyhydric alcohols, including sugars and sugar alcohols such as monoand poly-amines derived from dextrose. sucrose, sorbitol, mannitoL-dulcitol, arabitol and the like; alkyl-amines such as butylamine, dimethylamine, ethylene diamine, diethylene triamine, triethylene tetra-amine, monomethyl'eth-.

ylene diamine,monoethyl diethylene tetra-amine,

aromatic and heterooyclic bases such as pyridine,

quinaldine,-piperidine, methylpyridine, and homologues and derivatives thereof, quaternary am-.

monium bases or hydroxides such as tetramethyl ammonium hydroxide, tetra-ethyl ammonium hydroxide, quaternary ammonium bases with dissimilar alkyl radicals such as methylsix carbon atoms and a hydrophile group, which organic interface modifying agents contain at leastone acid function in unesterifled form which retains its salt-forming capacity, which includes the steps of reacting an organic nitrogenous base, an organic interface modifying-agent having alipophile group with at least six carbon atoms and a hydrophile group, said hydrophile group containing a replaceable potassium cation, and tartaric acid, whereby a precipitate is formed, and then separating said precipitate from the solution. v

3. The method of "preparing organic nitrogenous base salts of organic interface modifying agents containing a lipophile group in the form of an aliphatic acid. having at least six carbon atoms and a member selected from the group consisting of hydrophfllic sulphate, sulphonate; and phosphate groups, which includes the steps, of reacting an organic nitrogenous base, an organic interface modifying agent containing a lipophile aliphatic acid group having at least'six dering and similar uses in the textile and related industries. They are useful as flotation agents in ore flotation and agglomeration practices;

Those which possess good lathering, sudsing and,

detergent properties have unusual utility for the shampooing or cleansing of hair, particularly when employed in'aqueous solutions containing at least about 5% by weight of said compounds.

They may also be used for the cleaning or brushing of teeth and in cosmetic preparations such as cold creams, vanishing creams, tissue creams. shaving creams 'of the brushless or lathering type, and the like.

The term "solution as employed'herein and inthe appended claims is employed in a broad sense to include not only true solutions but also colloidal dispersions.

- The term higher, as employed herein, is in tended to mean not lessthan six carbon atoms and, concomitantly, the term ,lower will be understood to mean less than six carbon atoms, unless otherwise specifically stated.

' The present application ,isa continuation-inpart of our prior application, Serial No. 190,034,

' filed February 11, 1938.

carbon atoms and a member selected from the group consisting of sulphate, sulphonate, and phosphate groups the acidic hydrogen of which is replaced by an alkali metal cation, and an acid'which reacts with said alkali metal cation of said interface modifying agent to produce a salt which is less soluble than the interface modifying agent "constituting one of the reactants whereby a precipitate is formed, and then separating said precipltate'from the solution.

4. The method'of claim 3 wherein said alkali metal cation is potassium.

, 5. The method of preparing interface modifying agents containing a fatty acid acyl radical having at least six carbon atoms and a sulphonic group, the hydrogen of the sulphonic" group being replaced by an organic nitrogenous base, which comprises providing a composition containingiwaterand a substantial 1 proportion of the potassium salt of an interface modifying agent containinga fatty acid acyl group ,with

' at least six carbon atoms and a sulphonic group,

the mixture, and removing the resulting precipi Y tate of' potassium acid tartrate,

What we claim as new and desire to protect f by Letters Patent of the United States is:

1. The method of preparing organic nitrogenous base salts of organic interface modifying agents, having a lipophile group with at least six carbon atoms and ahydrophile group, which organic interface modifying agents contain at 6. The method of preparing interface modify ing agents containing a fatty acid acyl radical hav'ingat least six. carbon'atoms and a sulphonic group, the hydrogen of the sulphonic group being replaced by an alkylolamine, which comprises the steps of reacting, in aqueous media, a potashaving a lipophile group with at least six carbon the reactants, whereby a precipitate is formed,

and then separating said precipitate from the solution. h

,2. The method of preparing organic nitrogenous base salts of organic interface modifying agents, having a lipophile group with ,at least slum salt-of an organic interface modifyin agent containing a fatty acid acyl group with atleast six carbon atoms and a sulphonic group, an 21-! kylolamine, and an acid whose potassium salt' is less water-soluble than the potassium salt of the interface modifying agent, whereby the more insoluble salt is precipitated, and then separating the precipitate from the solution.

7. The method of preparing organic nitrogenous base salts of chemical compounds corresponding to the general formula:

' no-(aik-nmm-co-zkxm 1 whereinR is an organic. radical containing at.

least four carbon atoms, alk and Z are each members selected from the class consisting of hydrocarbon radicals and substitution products there'- of, Y is amember selected from the group consisting of hydrogen, 'alkyl. cycloalykl, alkoml,

aralkyL- ar'yl, and alkylol, m and 10' are whole numbers, an x is a sulphonic radical, which comprises the steps of reacting, in aqueous media, a potassium salt of the chemical compounds defined by said general formula, tartaric acid, and an organic nitrogenous base, and separating the resulting precipitate of potassium acid tartrate.

8. The method of claim 7 wherein the organic nitrogenous base is an alkylolamine.

9. The method of preparing organic nitrogenous base salts of chemical compounds corresponding to the general formula:

wherein is the acyl radical of a fatty acid containing from eight to eighteen carbon atoms, which comprises the steps of reacting, in aqueous media, a compound defined by said general formula, tartaric acid, and an organic nitrogenous base, and separating the resulting precipitate of potassium acid tartrate.

10. The method of claim 9 wherein the organic nitrogenous base comprises monoethanolamine.

11. The method of preparing the monoethanolamine salt of the sulpho-acetic acid amide of the lauric acid ester of monoethanolamine which comprises providing a compq'sltion containing water and a substantial proportion of the potassium salt of the sulpho-acetic acid amide of the lauric acid ester of monoethanolamine, adding an aqueous solution containing tartaric acid and monoethanolamine, stirring the mixture at a temperature of about 90 degrees C., and removing the resulting precipitate of potassium acid tartrate after cooling said mixture.

12. The method of preparing derivatives in the form of interface modifying agents of the group consisting of sulphates, sulphonates, and phosphates of compounds containing a fatty acid radical with at least six carbon atoms, the acidic hydrogen of the sulphate, sulphonate, or phosphate group of which is replaced by an organic nitrogenous base, which includes the steps of reacting, in aqueous media, an organic nitrogenous base, tartaric acid, and a derivative selected from the group consisting of potassium salts of sulphates, sulphonates and phosphates of compounds containing a fatty acid group with at least six carbon atoms, and removing the resulting precip itate of potassium acid tartrate 13. The method of claim 12 wherein the organic nitrogenous base is an alcohol amine.

14. The method of preparing organic nitrogenous base salts of derivatives of the group consisting of sulphates, sulphonates, and phosphates of chemical compounds containing a fatty acid ester group, the fatty acid radical of which contains from twelve to eighteen carbon atoms, the

acidic hydrogen of the sulphate, sulphonate, or

"phosphate group of which is replaced by an organic nitrogenous base, which includes the steps of reacting, in aqueous media, an organic nitrogenous base, tartaric acid, and a derivative selected from the group consisting of potassium salts of sulphates, sulphonates, and phosphates of chemical compounds containing a fatty acid ester group, the fatty acid radical of which contains from twelve to eighteen carbon atoms, and removing the resulting precipitate of potassium acid tartrate.

15. The method of claim 14 wherein the derivatives which are reacted to produce the organic nitrogenous base salts thereof comprise potassium salts of chemical compounds corresponding to the general formula:

Y RCO--alki I-CZX It I! wherein is an aliphatic acyl radical containin at least twelve carbon atoms, all: is hydrocarbon, Y is a member selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxyl, aralkyl, aryl, and alkylol, Z is a hydrocarbon residue and X is a sulphonic radical.

16. The method of preparing organic nitrogenous base salts of chemical compounds corresponding to'the general formula:

wherein 0 ll R-C- is the acyl radical of a fatty acid containing from eight to eighteen carbon atoms, which comprises the steps of reacting, in aqueous media, a compound defined by said general formula, tartaric acid, and an organic nitrogenous base, and sep-v arating the resulting precipitate of potassium acid tartrate.

17. The method of preparing monoethanolamine salts of a chemical compound corresponding to the formula which comprises the steps of reacting, in aqueous media, the compound defined by said formula, tartaric acid, and monoethanolamine, and separating the resulting precipitate of potassium acid tartrate.

FRANK J. CAHN. MORRIS B. KATZMAN. 

